US11993753B2 - Antifoulant formulation comprising an alkylbenzene sulfonate salt and polyisosuccininic anhydride combination and applications thereof - Google Patents

Antifoulant formulation comprising an alkylbenzene sulfonate salt and polyisosuccininic anhydride combination and applications thereof Download PDF

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US11993753B2
US11993753B2 US17/615,434 US202017615434A US11993753B2 US 11993753 B2 US11993753 B2 US 11993753B2 US 202017615434 A US202017615434 A US 202017615434A US 11993753 B2 US11993753 B2 US 11993753B2
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antifoulant
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sulphonic acid
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Doni ESWARARAO
Kanala RAGHAVA KRISHNA
Madala Sairamu
Mangala RAMKUMAR
Bojja Ramachandrarao
Nettam Venkateswarlu Choudary
Gandham SRIGANESH
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Hindustan Petroleum Corp Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • the present disclosure relates to the field of hydrocarbon refining.
  • it pertains to antifouling formulations for reducing fouling in heat exchangers.
  • the present disclosure further relates to a process for preparing the antifouling formulations and the method of inhibiting fouling in a hydrocarbon medium.
  • fouling The accumulation of unwanted materials on heat transfer surfaces is called fouling. It is a dynamic phenomenon which changes with time and may have a significantly negative impact on the thermal and mechanical performance as well as the operational efficiency of units, such as crude preheat exchangers, furnaces, hydrotreater exchangers, reactor beds, fluid catalytic cracking unit (FCCU) slurry exchangers and thermal cracking process exchangers.
  • FCCU fluid catalytic cracking unit
  • fouling deposits can be scale, suspended solids, and insoluble salts.
  • the fouling deposits can be categorized into two major types, inorganic and organic.
  • inorganic fouling corrosion of process equipment will form ferrous-based corrosion products such as iron sulfide or ferric oxide which will deposit in exchangers, mainly in areas with lower velocities.
  • Solid inorganic contaminants such as sand and silt can also deposit in the exchanger and cause hydraulic or thermal obstructions.
  • Organic fouling in a crude unit results from the precipitation of organic components, such as, asphaltenes, high molecular weight hydrocarbons which become insoluble in the system.
  • the asphaltenes become unstable because of the blending of incompatible crudes and get precipitated out due to high heating temperatures of crudes. Further, the asphaltenes and other heavier organic molecules are known to thermally degrade to coke when exposed to high heater tube surface temperatures.
  • Organic fouling is usually caused by polymerization reactions initiated by fouling precursors that are present in crude.
  • Two polymerization mechanisms have been identified, “free radical” and “non-free radical” reactions.
  • the most common mechanism is “free radical” polymerization, where unsaturated components, such as olefins and diolefins, react to form longer chain molecules. The molecule chain length increases to the point that solubility is exceeded, and deposition occurs.
  • Non-free radical polymerization mechanism occurs mainly as a result of condensation reactions involving components such as carboxylic acid and nitrogen compounds etc. To properly control fouling, the differences between these two categories must be thoroughly understood and accounted for when identifying the fouling mechanisms.
  • Fouling of refinery process equipment is a common problem resulting in severe economic penalties due to energy loss and has significant safety concerns.
  • antifoulant formulations comprising antifouling formulations comprising of ionic surfactants based on alkylbenzene sulfonates are known in the literature, such as U.S. Pat. Nos. 2,976,211, 3,080,280, 5,110,997, and WO 2017141077, etc.
  • a single antifouling formulation working on all types of crudes, crude blends, short residue and other refinery streams and units e.g., diesel hydrodesulfurization, i.e. DHDS unit
  • heat exchangers e.g., diesel hydrodesulfurization, i.e. DHDS unit
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkyl amine.
  • a process of preparing the antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkyl amine, the process comprising: (a) contacting at least one ammonium salt of linear alkyl benzene sulphonic acid, at least one aromatic hydrocarbon, at least one diluent, polyisobutylene succinic anhydride; and, at least one alkyl amine to obtain a first mixture; and (b) processing the first mixture to obtain the antifoulant formulation.
  • a method of inhibiting fouling in a liquid hydrocarbon medium comprising contacting the antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkyl amine, and the liquid hydrocarbon medium in the preheat exchangers of crude and short residue.
  • FIG. 1 illustrates the graphical representation of the evaluation of Crude-1 against antifoulant formulation, in accordance with an implementation of the present disclosure.
  • API is a commonly used index of the density of crude oil or refined products. API stands for the American Petroleum Institute, which is the industry organization that created this measure.
  • ambient in the present disclosure refers to a temperature in the range of 25° C. to 37° C.
  • Molar equivalent ratios of components may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • a temperature range of about 40° C. to about 50° C. should be interpreted to include not only the explicitly recited limits of about 40° C. to about 50° C., but also to include sub-ranges, such as 45° C. to 48° C., and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 42.2° C., 40.6° C., and 49.3° C., for example.
  • the present disclosure provides antifouling formulations comprising (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkyl amine.
  • the present antifoulant formulations when evaluated for a series of crudes and vacuum residue using refinery fouling process simulator (RFPS) showed excellent results compared to control experiments without the antifoulant formulation.
  • RFPS refinery fouling process simulator
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkyl amine.
  • an antifoulant formulation as described herein wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the at least one aromatic hydrocarbon weight ratio is in the range of 1:1-10:1.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkyl amine, wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the at least one aromatic hydrocarbon weight ratio is in the range of 1:1-10:1.
  • an antifoulant formulation as described herein wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the polyisobutylene succinic anhydride weight ratio is in the range of 0.25:1-10:1. In another embodiment of the present disclosure, the at least one ammonium salt of linear alkyl benzene sulphonic acid to the polyisobutylene succinic anhydride weight ratio is in the range of 0.25:1-4:1. In yet another embodiment of the present disclosure, the at least one ammonium salt of linear alkyl benzene sulphonic acid to the polyisobutylene succinic anhydride weight ratio is in the range of 0.25:1-2.5:1.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkylamine, wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the polyisobutylene succinic anhydride weight ratio is in the range of 0.25:1-10:1.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkylamine, wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the polyisobutylene succinic anhydride weight ratio is in the range of 0.25:1-4:1.
  • an antifoulant formulation as described herein, wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the at least one alkyl amine weight ratio is in the range of 1:1-20:1.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkylamine, wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the at least one alkyl amine weight ratio is in the range of 1:1-20:1.
  • an antifoulant formulation as described herein wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the at least one diluent weight ratio is in the range of 0.05:1-0.4:1.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkylamine, wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the at least one diluent weight ratio is in the range of 0.05:1-0.4:1.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkylamine, wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the at least one aromatic hydrocarbon weight ratio is in the range of 1:1-10:1, the at least one ammonium salt of linear alkyl benzene sulphonic acid to the polyisobutylene succinic anhydride weight ratio is in the range of 0.25:1-10:1, the at least one ammonium salt of linear alkyl benzene sulphonic acid to the at least one alkyl amine weight ratio is in the range of 1:1-20:1, and the at least one ammonium salt of linear alkyl benzene sulphonic acid to
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkylamine, wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid to the at least one aromatic hydrocarbon weight ratio is in the range of 1:1-10:1, the at least one ammonium salt of linear alkyl benzene sulphonic acid to the polyisobutylene succinic anhydride weight ratio is in the range of 0.25:1-4:1, the at least one ammonium salt of linear alkyl benzene sulphonic acid to the at least one alkyl amine weight ratio is in the range of 1:1-20:1, and the at least one ammonium salt of linear alkyl benzene sulphonic acid to the
  • an antifoulant formulation as described herein, wherein the at least one ammonium salt of linear alkyl benzene sulphonic acid has a weight percentage in the range of 5-20% with respect to the formulation; the at least one aromatic hydrocarbon has a weight percentage in the range of 2-5% with respect to the formulation; the at least one diluent has a weight percentage in the range of 50-85% with respect to the formulation; the polyisobutylene succinic anhydride has a weight percentage in the range of 5-20% with respect to the formulation; the at least one alkyl amine has a weight percentage in the range of 1-5% with respect to the formulation.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid having a weight percentage in the range of 5-20% with respect to the formulation; (b) at least one aromatic hydrocarbon having a weight percentage in the range of 2-5% with respect to the formulation; (c) at least one diluent having a weight percentage in the range of 50-85% with respect to the formulation; (d) polyisobutylene succinic anhydride having a weight percentage in the range of 5-20% with respect to the formulation; and (e) at least one alkyl amine having a weight percentage in the range of 1-5% with respect to the formulation.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid having a weight percentage in the range of 10-20% with respect to the formulation; (b) at least one aromatic hydrocarbon having a weight percentage in the range of 2.5-3.5% with respect to the formulation; (c) at least one diluent having a weight percentage in the range of 60-85% with respect to the formulation; (d) polyisobutylene succinic anhydride having a weight percentage in the range of 5-15% with respect to the formulation; and (e) at least one alkyl amine having a weight percentage in the range of 1-3% with respect to the formulation.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid having a weight percentage in the range of 10% with respect to the formulation; (b) at least one aromatic hydrocarbon having a weight percentage in the range of 3% with respect to the formulation; (c) at least one diluent having a weight percentage in the range of 75% with respect to the formulation; (d) polyisobutylene succinic anhydride having a weight percentage of 5% with respect to the formulation; and (e) at least one alkyl amine having a weight percentage in the range of 3% with respect to the formulation.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid having a weight percentage in the range of 10% with respect to the formulation; (b) at least one aromatic hydrocarbon having a weight percentage in the range of 3% with respect to the formulation; (c) at least one diluent having a weight percentage in the range of 75% with respect to the formulation; (d) polyisobutylene succinic anhydride having a weight percentage of 10% with respect to the formulation; and (e) at least one alkyl amine having a weight percentage in the range of 3% with respect to the formulation.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid having a weight percentage in the range of 20% with respect to the formulation; (b) at least one aromatic hydrocarbon having a weight percentage in the range of 3% with respect to the formulation; (c) at least one diluent having a weight percentage in the range of 65% with respect to the formulation; (d) polyisobutylene succinic anhydride having a weight percentage of 10% with respect to the formulation; and (e) at least one alkyl amine having a weight percentage in the range of 2% with respect to the formulation.
  • an antifoulant formulation as described herein wherein the at least one aromatic hydrocarbon is naphthalene, wherein naphthalene may be optionally substituted with C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 3-6 cycloalkyl, or C 5-6 aryl.
  • the at least one aromatic hydrocarbon is naphthalene.
  • an antifoulant formulation as described herein wherein the at least one diluent is selected from the group consisting of light cycle oil, kerosene, aromatic-rich hydrocarbon diluents, diesel, mineral turpentine oil (MTO), and combinations thereof.
  • the at least one diluent is light cycle oil.
  • the at least one diluent is kerosene.
  • an antifoulant formulation as described herein wherein the at least one alkylamine is selected from the group consisting of C 12 amine, C 8 amine, C 9 amine, C 10 amine, C 11 amine, C 13 amine, C 14 amine, C 16 amine, C 17 amine, C 18 amine, and combinations thereof.
  • the at least one alkylamine is C 12 amine.
  • the at least one alkylamine is lauryl amine.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon is naphthalene, wherein naphthalene may be optionally substituted with C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 3-6 cycloalkyl, or C 5-6 aryl; (c) at least one diluent selected from the group consisting of light cycle oil, kerosene, aromatic-rich hydrocarbon diluents, diesel, mineral turpentine oil (MTO), and combinations thereof; (d) polyisobutylene succinic anhydride; and (e) at least one alkyl amine selected from the group consisting of Cu amine, C 8 amine, C 9 amine, C 10 amine, C 11 amine, C 13 amine
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon is naphthalene; (c) at least one diluent selected from light cycle oil, or kerosene; (d) polyisobutylene succinic anhydride; and (e) at least one alkyl amine is C 12 amine.
  • an antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid having a weight percentage in the range of 5-20% with respect to the formulation; (b) at least one aromatic hydrocarbon is naphthalene, wherein naphthalene may be optionally substituted with C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 3-6 cycloalkyl, or C 5-6 aryl, and having a weight percentage in the range of 2-5% with respect to the formulation; (c) at least one diluent selected from the group consisting of light cycle oil, kerosene, aromatic-rich hydrocarbon diluents, diesel, mineral turpentine oil (MTO), and combinations thereof, and having a weight percentage in the range of 50-85% with respect to the formulation; (d) polyisobutylene
  • a process of preparing the antifoulant formulation as described herein comprising: (a) contacting at least one ammonium salt of linear alkyl benzene sulphonic acid, at least one aromatic hydrocarbon, at least one diluent, polyisobutylene succinic anhydride; and, at least one alkyl amine to obtain a first mixture; and (b) processing the first mixture to obtain the antifoulant formulation.
  • processing the first mixture is carried out a temperature in the range of 40-50° C. for a period in the range of 2-4 hours at a stirring speed in the range of 50-200 rpm to obtain the antifoulant formulation.
  • a process of preparing the antifoulant formulation as described herein comprising: (a) contacting at least one ammonium salt of linear alkyl benzene sulphonic acid, at least one aromatic hydrocarbon, at least one diluent, polyisobutylene succinic anhydride; and, at least one alkyl amine to obtain a first mixture; and (b) processing the first mixture at a temperature in the range of 40-50° C. for a period in the range of 2-4 hours at a stirring speed in the range of 50-200 rpm to obtain the antifoulant formulation.
  • a method of inhibiting fouling in a liquid hydrocarbon medium comprising contacting the antifoulant formulation as described herein and the liquid hydrocarbon medium in the preheat exchangers of crude and short residue.
  • a method of inhibiting fouling in a liquid hydrocarbon medium comprising contacting the antifoulant formulation as described herein and the liquid hydrocarbon medium, wherein the antifoulant formulation and the liquid hydrocarbon medium weight ratio is in the range of 1:500-1:200000.
  • the antifoulant formulation and the liquid hydrocarbon medium weight ratio is in the range of 1:500-1:20000.
  • the antifoulant formulation and the liquid hydrocarbon medium weight ratio is in the range of 1:500-1:2000.
  • the antifoulant formulation and the liquid hydrocarbon medium weight ratio is in the range of 1:500-1:1500.
  • the antifoulant formulation and the liquid hydrocarbon medium weight ratio is in the range of 1:500-1:1000.
  • a method of inhibiting fouling in a liquid hydrocarbon medium comprising contacting the antifoulant formulation comprising: (a) at least one ammonium salt of linear alkyl benzene sulphonic acid; (b) at least one aromatic hydrocarbon; (c) at least one diluent; (d) polyisobutylene succinic anhydride; and (e) at least one alkylamine, and the liquid hydrocarbon medium at a temperature in the range of 350° C. to 550° C. and a pressure in the range of 250 psi to 550 psi, wherein the temperature of the liquid hydrocarbon medium is in the range of 25° C. to 160° C. and the flow rate of the liquid hydrocarbon medium is in the range of 1-3 ml/min.
  • a method of inhibiting fouling in a liquid hydrocarbon medium comprising contacting the antifoulant formulation and the liquid hydrocarbon medium in the preheat exchangers of crude and/or short residue as described herein, wherein the antifoulant formulation and the liquid hydrocarbon medium weight ratio is in the range of 1:500-1:200000.
  • a method of inhibiting fouling in a liquid hydrocarbon medium comprising contacting the antifoulant formulation and the liquid hydrocarbon medium in the preheat exchangers of crude and/or short residue as described herein, wherein the antifoulant formulation and the liquid hydrocarbon medium weight ratio is in the range of 1:500-1:200000.
  • Fouling scales obtained from heat exchangers were studied, and the study showed that fouling scales contain both inorganic species and organic species. Therefore, the possibilities wherein a formulation could work on quenching the organic and inorganic fouling species were explored.
  • Fouling in heat exchangers are also affected by the type of crude and its constituents. Therefore, different crudes were analyzed for sulfur (wt %), total basic number (TBN) and saturates, aromatics, resins, asphaltenes (SARA) for asphaltene content. These factors were taken into consideration while developing the antifoulant formulations. The analysis of the different crudes concerning its content is displayed in Table 1 below.
  • Blend-2 Crude Sulfur Basic Asphaltene S. No. Name API (wt %) Nitrogen (wt %) 1 Crude-1 38.9 1.07 125 1.59 2 Crude-2 40.5 1.09 147 0.19 3 Crude-3 36.3 0.14 138 0.22 4 Crude-4 29.4 2.78 460 2.95 5 Blend-1 31.2 2.4 411 2.7 6 Blend-2 32.6 2.25 369 2.1 7 Blend 3 10.1 6.39 — 5.87 (short residue)
  • Blend-3 The analysis of the short residue blend, which is Blend-3 concerning its properties is displayed in Table 2 below.
  • Linear alkyl benzene sulfonic acid (LABSA) (1 mmol) was added to 2-neck round bottom flask with the condenser. The flask was cooled to 15° C. Morpholine (1.5 mmol) was added slowly while stirring the reaction contents. During the morpholine addition, care was taken so that the temperature inside the flask did not exceed 50° C. After completion of the morpholine addition, the resulting mixture was continued stirring for 30 minutes to afford LAB SA-Morpholine salt.
  • LABSA Linear alkyl benzene sulfonic acid
  • Linear alkyl benzene sulfonic acid (LABSA) (1 mmol) was added to 2-neck round bottom flask with the condenser. The flask was cooled to 15° C. Isopropylamine (IPA) (1.5 mmol) was added slowly while stirring the reaction contents. During the IPA addition, care was taken so that the temperature inside the flask did not exceed 25° C. This avoids vaporization of IPA. After completion of the IPA addition, the resulting reaction mixture was continued stirring for 30 minutes to afford LABSA-IPA salt.
  • LABSA-IPA salt Linear alkyl benzene sulfonic acid
  • LABSA-amine salt [5-20 wt %], naphthalene [2-5 wt %], polyisobutylene succinic anhydride (PIBSA) [5-20 wt %], lauryl amine [2-5 wt %] and diluent (light cycle oil for AF-15, AF-18, AF-19, AF-20, AF-21 and AF-24 (or) kerosene for AF-29, AF-30 and AF-36) [50-85 wt %] were blended while stirring between 40-50° C. The resulting reaction contents were stirred to obtain a homogeneous formulation (first mixture).
  • PIBSA polyisobutylene succinic anhydride
  • diethanolamine or monoethanolamine (0.1-2 wt %) were added, if required, at temperature in the range of 40-50° C. for a period in the range of 2-4 hours at a stirring speed in the range of 50-200 rpm to obtain the antifoulant formulation.
  • diethanolamine or monoethanolamine (0.1-2 wt %) were added, if required, at temperature in the range of 40-50° C. for a period in the range of 2-4 hours at a stirring speed in the range of 50-200 rpm to obtain the antifoulant formulation.
  • Several formulations were made with varying quantities of chemical constituents and diluents to evaluate various crudes, crude blends and vacuum residue/short residue.
  • Example 4 Method of Inhibiting Fouling of Hydrocarbon Medium Involving the Antifoulant Formulations and Evaluation Thereof
  • a method comprising contacting the antifoulant formulation, wherein the antifoulant formulation (having a weight percentage in the range of 0.1 to 0.15% corresponding to 1000-1500 ppm) and the liquid hydrocarbon medium (Crudes 1-4 and Blend 1-3) weight ratio is in the range of 1:600-1:1000 was performed in the laboratory.
  • the operating conditions and parameters applied to evaluate fouling inhibition of a hydrocarbon medium by the antifoulant formulation of the present disclosure have been provided in Table 3 below.
  • RPFS Refinery Process Fouling Simulator
  • the performance monitoring of the antifoulant formulations of the present disclosure was performed for different crudes and blends in terms of ⁇ T (difference of temperature).
  • ⁇ T difference of temperature
  • LCO Light Cycle Oil
  • kerosene and/or highly aromatic-rich hydrocarbon having up to 55% aromatics were used as the diluents in the antifoulant formulations of the present disclosure.
  • AF-15 Various antifoulant formulations, such as, AF-15, AF-18, AF-19, AF-20, and AF-21 were mixed with crude 1 to evaluate the antifoulant efficacy.
  • the AF-15 formulation contained 15% by weight of ammonium salt of linear alkyl benzene sulphonic acid, 2% by weight of alkyl amine, and 83% by weight of the diluent.
  • the aromatic hydrocarbon and polyisobutylene succinic anhydride were absent in the formulation AF-15.
  • the formulation AF-18 contained 10% by weight of ammonium salt of linear alkyl benzene sulphonic acid, 5% by weight of polyisobutylene succinic anhydride, and 85% by weight of the diluent.
  • the aromatic hydrocarbon and alkyl amine were absent in the formulation AF-18.
  • two out of the five constituents mentioned in the present disclosure were absent in the Formulations AF-15 and AF-18.
  • the formulation AF-19 consisted of 10% by weight of ammonium salt of linear alkyl benzene sulphonic acid, 5% by weight of polyisobutylene succinic anhydride, 2% by weight of alkyl amine, and 83% by weight of the diluent.
  • the aromatic hydrocarbon was absent in AF-19.
  • the formulation AF-20 comprised of 10% by weight of polyisobutylene succinic anhydride, 3% by weight of aromatic hydrocarbon, 2% by weight of alkyl amine, and 85% by weight of the diluent, linear alkyl benzene sulphonic acid is absent.
  • the polyisobutylene succinic anhydride is out of the specified range (5-20 wt %) in the formulations AF-18 and AF-19.
  • the antifoulant formulation AF-21 has all the five components described in the present disclosure.
  • the formulation comprised 10% by weight of ammonium salt of linear alkyl benzene sulphonic acid, 10% by weight of polyisobutylene succinic anhydride, 3% by weight of aromatic hydrocarbon, 2% by weight of alkyl amine, and 75% by weight of the diluent.
  • the efficacy of all the antifoulant formulations were tested in terms of the ⁇ T values for Crude 1. The lower the value of ⁇ T, the better was the performance.
  • the ⁇ T values for the formulations AF-15, AF-18, AF-19 and AF-20 which do not have all the five components were found to have a high ⁇ T value when compared with the antifoulant formulation AF-21 which had all the five components.
  • the ⁇ T value attained for AF-21 was ⁇ 14.6° C., which was the lowest when compared the control crude-1 without antifoulant formulation of the present disclosure (AF-21).
  • Additional set of antifoulant formulations were prepared, such as, AF-24, AF-29, AF-30, and AF-36, and evaluated for their antifoulant efficacy against Blend-3.
  • the efficacy results of the various antifoulant formulation against Blend-3 containing short residue (SR) is further tabulated in Table 5 below.
  • the AF-24 (composition provided below in Table 5) formulation contained only two components out of five, namely, 20% by weight of ammonium salt of linear alkyl and 80% by weight of the diluent (light cycle oil).
  • the components alkyl amine, aromatic hydrocarbon, and polyisobutylene succinic anhydride were absent.
  • AF-30 comprised only three out of five components, i.e., 20% by weight of ammonium salt of linear alkyl, 5% by weight of polyisobutylene succinic anhydride and 75% by weight of the diluent.
  • the components alkylamine, and aromatic hydrocarbon were absent.
  • the antifoulant formulation AF-29 contained all the five components, i.e., 20% by weight of ammonium salt of linear alkyl benzene sulphonic acid, 5% by weight of polyisobutylene succinic anhydride, 3% by weight of aromatic hydrocarbon, 2% by weight of alkyl amine and 70% by weight of the diluent.
  • AF-36 contained all the five components, viz., 20% by weight of ammonium salt of linear alkyl benzene sulphonic acid, 10% by weight of polyisobutylene succinic anhydride, 3% by weight of aromatic hydrocarbon, 2% by weight of alkylamine and 65% by weight of the diluent.
  • Blend-3 ⁇ T (° C.) LABSA-amine Long chain amine for Blend-3 Formulation salt PIBSA Naphthalene (lauryl amine) Diluent (SR) Without (w/o) using — — — — — — ⁇ 32.7
  • Antifoulant formulation AF-24 20% — — — — 80% ⁇ 20.9 LCO AF-29 20 wt % 5 wt % 3 wt % 2 wt % 70 wt % ⁇ 19.7 kerosene AF-30 20% 5 wt % — — 75% ⁇ 26.2 kerosene AF-36 20% 10% 3 wt % 2% 65% ⁇ 17 kerosene
  • the present disclosure further illustrates the evaluation of the antifoulant formulation of the present disclosure against other crudes (Crude-2 and Crude-3) and blends (Blend-1 and Blend-2) concerning their ⁇ T values.
  • the antifouling formulation of the present disclosure is able to arrest almost all types of fouling to merit as effective antifouling formulation which has been validated by testing various crudes and blends. Therefore, the antifoulant formulation of the present disclosure is technically advanced over the antifoulant formulations known in the art.
  • the present disclosure provides a high-performance antifoulant formulation comprising ionic surfactants based on alkylbenzene sulfonates and amines, polyisobutylene succinic anhydride, naphthalene, and aromatic-rich diluents, for reducing fouling, including particulate-induced fouling, in heat exchangers of crude and vacuum residue in the hydrocarbon refining process.
  • the antifoulant formulation of the present disclosure when evaluated for a series of crudes and vacuum residue using refinery process fouling simulator (RPFS) showed excellent results compared to corresponding runs without antifoulant formulations.
  • RPFS refinery process fouling simulator
  • the evaluation studies are not only limited to the heat exchangers of crudes, blends and short residue but can also be used in the heat exchangers of DHDS unit, vis-breaker units, and other refinery applications.

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2976211A (en) 1958-02-21 1961-03-21 Witco Chemical Corp Dispersant compositions and toxicant concentrates containing the same
US3080280A (en) 1961-03-20 1963-03-05 Witco Chemical Corp Dispersant compositions and toxicant concentrates containing the same
GB1139172A (en) 1966-01-28 1969-01-08 Monsanto Chemicals Process for the production of oil solutions of sulphonate/carbonate complexes
US5110997A (en) 1991-04-19 1992-05-05 Exxon Chemical Patents Inc. Process for preventing fouling in the production of ethylene dichloride
CN101318916A (zh) 2008-06-20 2008-12-10 辽宁天合精细化工股份有限公司 一种高碱值(tbn300)合成烷基苯磺酸钙的制备方法
US20150218468A1 (en) * 2014-02-05 2015-08-06 Baker Hughes Incorporated Antifoulants for use in hydrocarbon fluids
WO2017141077A1 (en) 2016-02-17 2017-08-24 Hindustan Petroleum Corporation Limited Composition and method for dispersing scales and solid deposits
US20180079977A1 (en) * 2016-09-16 2018-03-22 Ecolab Usa Inc. Fatty alcohols and esters for crude oil treatment
US20190203131A1 (en) * 2016-08-25 2019-07-04 General Electric Company Reduced fouling of hydrocarbon oil

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITRM20120162A1 (it) 2012-04-16 2013-10-17 Marcello Ferrara Metodo e impianto per il trattamento di apparecchiature petrolifere

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2976211A (en) 1958-02-21 1961-03-21 Witco Chemical Corp Dispersant compositions and toxicant concentrates containing the same
US3080280A (en) 1961-03-20 1963-03-05 Witco Chemical Corp Dispersant compositions and toxicant concentrates containing the same
GB1139172A (en) 1966-01-28 1969-01-08 Monsanto Chemicals Process for the production of oil solutions of sulphonate/carbonate complexes
US5110997A (en) 1991-04-19 1992-05-05 Exxon Chemical Patents Inc. Process for preventing fouling in the production of ethylene dichloride
CN101318916A (zh) 2008-06-20 2008-12-10 辽宁天合精细化工股份有限公司 一种高碱值(tbn300)合成烷基苯磺酸钙的制备方法
US20150218468A1 (en) * 2014-02-05 2015-08-06 Baker Hughes Incorporated Antifoulants for use in hydrocarbon fluids
WO2017141077A1 (en) 2016-02-17 2017-08-24 Hindustan Petroleum Corporation Limited Composition and method for dispersing scales and solid deposits
US20190078030A1 (en) * 2016-02-17 2019-03-14 Hindustan Petroleum Corporation Limited Composition and method for dispersing scales and solid deposits
US20190203131A1 (en) * 2016-08-25 2019-07-04 General Electric Company Reduced fouling of hydrocarbon oil
US20180079977A1 (en) * 2016-09-16 2018-03-22 Ecolab Usa Inc. Fatty alcohols and esters for crude oil treatment

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Antifoulant for Ethylene Dichloride Processing", Research Disclosure, Kenneth Mason Publications, Hampshire, UK, GB, vol. 356, No. 28, Dec. 1, 1993; XP007119505; 3 pgs.
International Search Report & Written Opinion for PCT/IB2020/050307 dated Jul. 17, 2020, 9 pgs.
XP007119505, Antifoulant for ethylene dichloride processing, Research Disclosure, Kenneth Mason Publications, Hampshire, UK, GB, vol. 356, No. 28, Dec. 1, 1993.

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